Substituted imidazolines



United States Patent 3,231,580 SUBSTITUTED IMIDAZOLINES Hans S.Mannheimer, Toms River, N.J., assignor to Hans S. Manuheimer and John J.McCahe, Jr., as joint venturers No Drawing. Filed June 30, 1961, Ser.No. 122,609

Claims. (Cl. 260309.6)

This invention relates to novel compounds and to methods for producingthem. In one of its more specific aspects this invention is directed tonovel amphoteric cycloimidines and to methods for making them.

The novel compounds of this invention are water-soluble, amphotericsurface active agents finding application in a wide variety of diiferentfields. They may be used as general purpose detergents, textile treatingagents, as emulsifying and emulgating agent. They also find em ploymentas components in cosmetic preparations, and due to their high foamingand other characteristics find use as components in various shampooformulations.

The compounds of the present invention are of the following generalFormula I and are also salts produced by reacting the same or differentspecies of said compounds with each other:

wherein R is a hydrocarbon radical of 418 carbon atoms; each R isselected from the group consisting of divalent saturated hydrocarbongroups, such as alkylene groups of 2-4 carbon atoms, which are C H -C Hand -C H M is hydrogen or its equivalent and preferably an alkali metalequivalent and for most purposes sodium or potassium, and x is 0-8.

The novel salts are produced by reacting under certain conditions of twoor more moles of compounds of Formula I wherein M attached to the S0group of 1 mole is replaced by another mole of such compound to replacethe OH group thereof attached directly to the nitrogen of said othermole.

While more than 3 moles of said compounds of Formula I may be reactedwith each other under certain con ditions, the following areillustrative examples of some of said salts when only 2 and 3 molesrespectively are reacted with each other and are known as Salts I and IIrespectively:

Said salts, examples of which are said Salts I and II, as distinguishedfrom internal salts, are external salts as shown in the illustrativestructural formulas thereof. Moreover they are self-salts in that two ormore moles 5 of the same specie of compounds of Formula I may be reactedwith each other to produce such external salts or 1 mole of a specie maybe reacted with 1 mole of a different specie of compounds of Formula Ito provide external self-salts of dilferent species coupled together forexample in the manner of Salts I and II. Of course, more than twodifferent species, as for Example 3 or more may be used if desiredthereby to provide external self-salts in which the resultant externalsalt such as Salt II may be produced, with all three dilferent speciesas reactants for the production thereof.

For the production of said novel compounds of For mula I, I employ asreactants my novel sultone described and claimed in my US. patentapplication Ser. No. 120,- 921, filed June 30, 1961, subsequently issuedas US. Patent 3,100,779, and of the following formula:

os02 (IE2 (IE2 OH (in and a cycloimidine of the following Formula II:

/ CHa Certain of said cycloimidine of Formula 11 may be produced byreacting one mole proportion of a monocarboxyiic acid, R-COOH, wherein Ris a hydrocarbon radical of 418 carbon atoms, with one mole proportionof diamine reactant such as amino ethyl ethanol amine (NH C H NHC H OH),amino ethyl propanol amine (NH C H NHC H OH) and amino ethyl butanolamine (NH C H NHC l-l OH) respectively to provide cycloimidines of thefollowing formula Y:

N/ CHz Rd; Ii -Y wherein Y is C H OH, C H OI-I or C H OH depending uponwhich of the aforesaid diamine reactants was employed.

The specific steps which may be used for carrying out said reaction forthe production of said compounds of formula Y are well known to thoseskilled in the art. Among some of the methods which may be employed forthat purpose are those described in my U.S. Patent 2,528,378, issued onOctober 31, 1950.

Still other cycloimidines of Formula Il. may be produced by reacting onemole proportion of a compound of formula Y with 1-8 moles proportion ofan allrylene oxide, such as ethylene oxide, propylene oxide or butyleneoxide in the manner known to the art thereby to provide a large numberof different compounds, specific examples of which are compounds thesame as the cyclo- 3 imidines of formula Y except that for the C H OH, CH OH or C H OH there is substituted specifically any of the following,for example,

Of course many other like groups containing more or less of alkyleneoxide than is present in the specific groups above set forth may besubstituted for said C H OH in formula Y.

The organic acid reacted with a diamine, examples of which arehereinbefore set forth, is one of 5-19 carbon atoms and containing asingle COOH group, or any of the available anhydrides of said acids andby the term monocarboxylic organic acid as used herein, I mean toinclude both the acid and the available anhydride thereof which I regardas the equivalent of the acid. These acids may be: the aliphatic openchain saturated or unsaturated fatty acids as well as said fatty acidscontaining substituents, such as aryl radicals, as for example, acids ofthe type of Twitchell fatty acids; cycloaliphatic carboxylic acidspreferably containing no more than 4 condensed nuclei and examples ofwhich are hexahydrobenzoic, resinic, and naphthenic acids; as well asaromatic and aromatic-aliphatic carboxylic acids, such as (C H CH COOH),etc.

While carboxylic acids having any number of carbon atoms may beemployed, I prefer to employ those having at least 5 carbon atoms andpreferably 5-19 carbon atoms in straight chain relationship. The acidswhich I' employ may be derived from a number of different sources. Amongsome of them are the acid components chosen from oil or fats of animal,marine or vegetable origin and these includes; the acids of coconut,palm kernel and palm oil, also of soy bean, linseed, olive, rapeseed,cottonseed, peanut and castor oil which contain large proportions ofunsaturated fatty acids and also the acids derived from tallow, fish andseal oils, whale or shark oils and the hydrogenated acids from thesesources. Moreover, the synthetic high molecular weight fatty acids,obtained by the oxidation of parafiin Wax and similar high molecularweight hydrocarbons by means of gaseous oxidizing agents may beemployed. In addition the acid may be one of the resinic acids, such asabietic acid, or the naphthenic acids-and long chain fatty acids havingan aromatic hydrocarbon radical connected directly with the aliphaticchain (Twitchell fatty acids) as are obtainable from oleic, ricinoleic,linoleic and similar unsaturated fatty acids. Instead of employingmixture of acids from oil, fats and resins, single acids may be used,for example caproic, pimelic, heptylic, caprylic, un-

decylic, lauric, palmitic, stearic, behenic, arachic, and

carotic, oleic, erucic, linoleic, linolenic, ricinoleic and stearicacids.

My novel sultone employed as a reactant herein may be prepared byemploying the procedure set forth in the following Example A, all partsbeing given by weight 'unless otherwise specified.

EXAMPLE A About 104 parts of sodium meta bisulfite Na S O were chargedinto a glass flask and then there was also charged into said flask 600parts of water into which was dissolved 1 cc. of a 50% aqueous solutionof NaOH thereby to dissolve said sodium meta bisulfite therein.

The solution was then heated to about C. and maintained at thattemperature for a period of about 15 minutes thereby to conveysubstantially all of the sodium meta bisulfite to sodium acid sulfite(NaHSO The reactant solution of sodium acid sulfite was cooled to about28 C. and by slow additions 101 parts of epichlorhydrin was addedthereto with constant stirring over a 45 minute period, and thetemperature of the mass throughout said period was controlled byexternal cooling thereby to maintain the temperature thereof at about4750 C. throughout said period. Thereafter and for the next 2 /2 hours,stirring of the mass was continued and its temperature maintained at47-50 C. Then with or without a reflux condenser coupled with saidflask, the mass therein while heated to boiling and maintained in thatcondition for a period of about 1 hour. Then the mass in said flask iscooled to room temperature, is hereinafter known as Mass A, and consistsessen- ,tially of an aqueous solution of the novel sultone, whosestructural formula is hereinbefore set forth, and NaCl byproduct.

According to this invent-ion said novel sultone may be reacted with oneor a combination of two or more of said cycloimidines of Formula II, inthe mole proportion of about 1 of sultone to 1 of said cycloim-idincs.-Said reaction is preferably carried out in an aqueous medium and withthe use of external heat to provide an aqueous solution of one or acombination of two or more compounds which are internal salts of thefollowing Formula III:

When a small quantity, as for example 1 cc. of said aqueous solution ofa compound of Formula III is added to cc. of clear tap Water and shakentherewith, there is a change from clear to cloudy. This indicates itslack of water-solubility in low concentration in which said compoundsnormally would be used, as surface active agents. I have discovered thatthe structures thereof may be changed thereby to convert and render themwater-soluble, in low concentrations, as well as high concentrations,amphoteric and further characterized by having good surface activity,detergent and wetting properties and useful in shampoos, cosmetics, inthe fields of treating of textiles, etc. I

For the aforesaid purpose the novel compounds of Formula III may underalkaline conditions in an aqueous medium be heated thereby to convertthem into said novel water-soluble amphoterics having the otherforegoing properties and being compounds of said Formula I which aresoluble in low and high concentrations in an aqueous medium whose pH maybe as low as 1 and as high as 14.

The alkaline agent preferably employed to render said aqueous mediumalkaline is an alkali metal'hydroxide, such as NaOH, KOH or the like andthe amount of said agent is preferably at least about 1 mole proportionthereof per mole proportion of said novel compounds of Formula III insaid aqueous medium.

I have also discovered that said novel water-soluble amphoteric surfaceactive agents may be self reacted in the presence of an acidic agent,such as hydrochloric, acetic, hydroxyacetic, phosphoric acids, etc., toprovide external self-reacted salts, such as Salts I and IIrespectively, for example, whose structural formulas are hereinbeforeset forth; and are given herein by way of illustration and notlimitation for the reason that more than 3 moles of compounds of FormulaI may be reacted with Said entire Mass A which is an aqueous solution ofmy novel sultone, in Example A herein is heated to 80 C. and while atthat temperature there are added with stirring 269 parts (1 mole) of acompound, hereinafter referredto as compound X, of the followingformula:

The resultant mass is then, while being stirred, allowed to standovernight in a room whose temperature is 20 C. The next morning, themass which has cooled to 20 C., While stirred, is heated to andmaintained to 80 C. about 3 hours, whereby there is produced an aqueoussolution having apI-I of 6.8 (electrically measured) of a compound ofthe following formula:

The aforesaid compound which is an internal salt is not water-soluble inlow concentrations. This is evidenced when one cc. of said aqueoussolution at the end of said 3 hour period is added to 100 cc. of cleartap water and shaken therewith it causes a change from clear to cloudy.

Then 88 parts of a 50% aqueous solution of NaOH is added slowly to saidentire aqueous mass after said 3 hour period while constant stirringstill is maintained and the entire mass is heated to and then maintainedat a temperature of 75-85 C. for a period of about 3 hours thereby toprovide an aqueous solution hereinafter known as Solution 1 consistingessentially of water in which are dissolved the NaCl byproduct and novelamphoteric l of the following formula:

Said amphoteric 1 is water-soluble even in very low concentrations asevidenced by adding 1 cc. of said Solution 1 to 100 cc. of water, whichremain clear after said addition.

EXAMPLES 2 AND 3 Employ the same procedure and components as set forthin Example 1, except that for the 269 parts of compound X employedtherein, there are substituted 251 parts (1 mole) of a capric acidderivative and 291 parts (1 mole) of a stearic acid derivative of aminoethyl ethanol amine respectively, which are the same as the compound Xexcept that the radical (C I-I thereof is replaced by the respectivecapryl (C H radical and the stearyl ((1 11 radical whereby there areproduced novel amphoterics 2 and 3 respectively, which are the same asamphoteric 1 except for the substitution of the C9H19 and C I-I radicalsrespectively for the C H radical of amphoteric 1.

EXAMPLES 4 AND Employ the same procedure and components as Example 1except that instead of the 269 parts of compound X of Example 1 thereare employed 284 and 395 parts respectively of the following respectivereactants:

and

to produce novel amphoterics 4 and 5 of the following respectiveformulas:

Employ the same procedure and components as those of Example 1 hereinexcept that for the 1 mole proportion of compound X, there may besubstituted .6 mole proportion of any other compound which is the sameas compound X, except that for the radical C H thereof, there issubstituted any other hydrocarbon radical of 4-18 carbon atoms and/ orfor the CH CH -OH group thereof there is substituted any of the othergroups hereinhefore defined and specific examples of which arehereinbefore set forth so that there are produced literally hundreds ofdifierent amphoterics which are of the same formula as amphoteric 1 ofsaid Example 1 herein except that for the radical C H thereof there issubstituted any other hydrocarbon radical of 4-18 caubon atoms, and/ orfor the radical CH CH OH thereof, there is substituted any of the otheraforesaid radicals R (OR O-H.

All of said novel amphoterics of Examples 1-5 and 6-on are water surfaceactive amphoterics having excellent water-solubility at high as well asvery low concentrations and in aqueous solution having good foamingproperties and find the uses hereinbefore set forth.

I have further discovered that said individual amphoteric compounds maybe reacted with themselves or with each other to provide salts thereof.For this purpose there is added to the aqueous solution of theamphoteric prepared according to any of said examples a quantity of anacidic agent, such as a HCl, to lower the pH thereof. In general, thequantity of HCl added is in the range of about /2 to 1 mole proportionof HCl per mole proportion of amphoteric of Formula I in solution. Thenthe aqueous mass is heated to 40-50 C. and maintained at thattemperature for about 5-10 minutes to provide the salts of theamphoteric employed, some general examples of such salts are said SaltsI and II whose structural formulas are hereinbefore set forth and otherof such salts in which more than three moles of the aniphoteric employedhave reacted to provide still longer chain salts than said Salt II. Thelength of the salt formation, examples of some of them being said SaltsI and II, are dependent upon the concentration of the novel amphetericsof Formula I in solution, the temperature of the mass, the quantity ofI-ICl employed, etc. In most instances the resultant salt formations aremixtures of salts of different lengths, all of which of course are saltsof at least 2 moles of the amphoteric used.

The following are illustrative methods for producing such salts and aregiven by way of illustration and not limitation, all parts being givenby weight unless otherwise specified.

EXAMPLE 1S The entire Solution 1 of Example '1 herein is heated to 40 C.and while at that temperature there is added thereto about 100 parts ofHCl (32% conc.) while strring.

The resultant mass is maintained at 40 C. while being constantly stirredfor a period of about -10 minutes. By virtue of the foregoing theamphoteric 1 in said solution is converted into its external salts ofthe type shown as Salts I and II herein and/or other salts of longerlengths but of the aforesaid type.

Sand external self-salts, like compounds of Formula I, are water-solublein low as well as high concentrations as evidenced by the fact that when1 cc. of said solution containing said salts is added to 100 cc. ofclear tap water and shaken therewith, clearness is maintained. Theaforesaid is not changed even when the pH of said solution is firstadjusted to 6.8 for comparative purposes.

If desired a mixture of two or more different ampholites, such as amixture of ampholites 1, 2 and 3 for example may be treated in the samemanner as above thereby to provide such salts of different ampholites,with ampholites 1 and 2, 2 and 3 and/or 1, 2 and 3, as well as 1 and l,2 and 2, and 3 and 3 being reacted with each other to provide salts ofthe type of Salts I and II heretofore shown structurally.

These external self-salts also have excellent water-solubilitycharacteristics in high and low concentration, in aqueous solution aregood foaming agents and have the same uses as the compounds of Formula Iherein.

It is significant that in the production of aqueous solutions ofcompounds of Formula III which have a pH of 6.8, an example of which issuch as solution thereof of Example 1 herein, that such solutions arenot water-soluble in low concentrations as hereinbefore set forth; whereas aqueous solutions of said external self-salts adjusted to acorresponding pH are water soluble in correspondingly lowconcentrations. The foregoing clearly establishes that the internalsalts of Formula III are different in character from the externalself-salts hereinbefore described and that the treatment of compounds ofFormula I results in the production of external self salts and not areversionto the internal salts.

As distinguished from the aforesaid my novel compounds of Formula I aswell as the external self-salts thereof are soluble in clear water toprovide clear solutions in all concentrations, that is highconcentrations as well as low concentrations of or less.

It is to be understood of course, that the respective definitions of R,R x and M are the same as they are used in the various formulas herein;and that wherever Na is used in any of the organic structural formulasin the description and claims herein, it is meant to cover its obviousequivalents, such as hydrogen, any other alkali metal or otherequivalents well known to the art which may be substituted therefor; andthat wherever caustic soda is employed in the description and claims, itis meant to cover its obvious equivalents, among which are KOH, as wellas other appropriate alkalies.

While fair yields of said novel compounds of Formula I may be obtainedby employing respective quantities of my novel sultone and compounds ofFormula II in the mole proportion of 1 to 1 as in Examples 1-3 herein,it is preferable that the mole ratio of the quantity of sulton'e to thequantity of compounds of Formula ll be about 12 moles and for mostpurposes 1.2-1.8 moles and more preferably approximately 1.5 moles ofsultone per mole of compound of Formula II employed, whereby highyields, measuring more than 90% of theoretical, of the novel amphotericsin aqueous solution may be obtained.

It is to be understood that the following claims are intended to covergeneric and specific features of the invention herein described and allstatements of the scope of the invention which as a matter of languagemight be said to fall therebetween, and that they are intended to beinclusive in scope and not exclusive in that, if desired, othermaterials may be added to my novel products herein claimed withoutdeparting from the spirit of the invention.

I claim:

1. A compound selected from the group consisting of (a) compounds and(b) external self salts of (a) of the formula:

wherein R is hydrocarbon of 4-18 carbon atoms, each R is saturatedhydrocarbon of 2-4 carbon atoms, x is 0-8 and M is selected from thegroup consisting of hydrogen and alkali metals and external self-salts.

2. A compound as defined in claim 1, and wherein R is only ethylenicallyunsaturated hydrocarbon of 4-18 carbon atoms.

3. A compound as defined in claim 1, and wherein R is alkyl of 4-18carbon atoms.

4. A compound of the formula:

wherein R is aliphatic hydrocarbon of 4-118 carbon atoms.

5. A compound of the formula:

References Cited by the Examiner UNITED STATES PATENTS OTHER REFERENCESGutmann: J our. Soc. Dyers and Colorists, vol. 75, No. 2, page 83(1959).

Helberger: Chem. Abstracts, vol. 41, C01. 4101 (1947).

Helberger et al.: German application 1,018,421, printed Oct. 31, 1957.

Schwartz et al.: Surface Active Ag'ents, pages 10, 218, and 225-227,Interscience, New York, 1949.

WALTER A. MODANCE, Primary Examiner.

DUVAL T. MCCUTCHEN, IRVING MARCUS,

Examiners.

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (A) COMPOUNDS AND(B) EXTERNAL SELF SALTS OF (A) OF THE FORMULA: